The photofragment excitation (PHOFEX) spectrum for O(1D) production from the photolysis of ozone under supersonic free-jet conditions was measured, scanning the photodissociation wavelength in the region of 305–329 nm and probing the O(1D) atoms by vacuum ultraviolet laser induced fluorescence at 115.2 nm. The bond dissociation energy D00(O2–O) was determined to be 101.53±0.25 kJ mol−1 from the cut-off wavelength in the PHOFEX spectrum for the photodissociation of jet-cooled ozone (Trot≈5 K) to O(1D)+O2(a 1Δg). The cut-off wavelength for vibrationally hot band excitation to the dissociative continuum of O(1D)+O2(a 1Δg) was also observed in the PHOFEX spectrum. It was found that the active mode for the hot band excitation was the antisymmetric stretching mode ν3 in the ground electronic state of ozone. Sharp peaks corresponding to vibrational bands in the Huggins system were also observed in the PHOFEX spectrum of the O(1D) atoms produced via the spin-forbidden dissociation process, O(1D)+O2(X 3g). The spectral widths of the vibronic bands in the Huggins system are discussed in terms of the dissociation dynamics.

1.
R. P. Wayne, Chemistry of Atmospheres, 2nd ed. (Oxford University Press, New York, 1991).
2.
H. Okabe, Photochemistry of Small Molecules (Wiley-Interscience, New York, 1978).
3.
J. I.
Steinfeld
,
S. M.
Adler-Golden
, and
J. W.
Gallagher
,
J. Phys. Chem. Ref. Data
16
,
911
(
1987
).
4.
G. K.
Moortgat
and
P.
Warneck
,
Z. Naturforsch
30a
,
835
(
1975
).
5.
I.
Arnold
,
F. J.
Comes
, and
G. K.
Moortgat
,
Chem. Phys.
24
,
211
(
1977
).
6.
J. C.
Brock
and
R. T.
Watson
,
Chem. Phys.
46
,
477
(
1980
).
7.
M.
Trolier
and
J. R.
Wisenfeld
,
J. Geophys. Res.
93
,
7119
(
1988
).
8.
S. M.
Ball
,
G.
Hancock
,
I. J.
Murphy
, and
S. P.
Rayner
,
Geophys. Res. Lett.
20
,
2063
(
1993
).
9.
H. A.
Michelsen
,
R. J.
Salawitch
,
P. O.
Wennberg
, and
J. G.
Anderson
,
Geophys. Res. Lett.
21
,
2227
(
1994
).
10.
W.
Amerding
,
F. J.
Comes
, and
B.
Schülke
,
J. Phys. Chem.
99
,
3137
(
1994
).
11.
S. M.
Ball
,
G.
Hancock
, and
F.
Winterbottom
,
Faraday Discuss. Chem. Soc.
100
,
215
(
1995
).
12.
S. M.
Ball
and
G.
Hancock
,
Geophys. Res. Lett.
22
,
1213
(
1995
).
13.
K.
Takahashi
,
Y.
Matsumi
, and
M.
Kawasaki
,
J. Phys. Chem.
100
,
4084
(
1996
).
14.
S. M.
Ball
,
G.
Hancock
,
J. C.
Pinot de Moira
,
C. M.
Sadowski
, and
F.
Winterbottom
,
Chem. Phys. Lett.
245
,
1
(
1995
).
15.
K.
Takahashi
,
M.
Kishigami
,
Y.
Matsumi
,
M.
Kawasaki
, and
A. J.
Orr-Ewing
,
J. Chem. Phys.
105
,
5290
(
1996
).
16.
A.
Kailen
and
S.
Jahn
,
Inorg, Chem.
68
,
243
(
1910
).
17.
P.
Günther
,
W.
Wassmuth
, and
L. A.
Schryver
,
Z. Phys. Chem.
158
,
297
(
1932
).
18.
M. W.
Chase
, Jr.
,
C. A.
Davies
,
J. R.
Downey
, Jr.
,
D. J.
Fruip
,
R. A.
McDonald
, and
A. N.
Syverud
, JANAF Thermochemical Tables,
J. Phys. Chem. Ref. Data
14
, Suppl.
1
(
1985
).
19.
R. K.
Sparks
,
L R.
Carlson
,
K.
Shobatake
,
M. L.
Kowalczyk
, and
Y. T.
Lee
,
J. Chem. Phys.
72
,
1401
(
1980
).
20.
D. S.
Moore
,
D. S.
Bomse
, and
J. J.
Valentini
,
J. Chem. Phys.
79
,
1745
(
1983
).
21.
M.-A.
Thelen
,
T.
Gejo
,
J. A.
Harrison
, and
J. R.
Huber
,
J. Chem. Phys.
103
,
7946
(
1995
).
22.
J. L.
Gole
and
R. N.
Zare
,
J. Chem. Phys.
57
,
5331
(
1972
).
23.
A.
Banichevich
,
S. D.
Peyerimhoff
, and
F.
Grein
,
Chem. Phys.
178
,
155
(
1993
).
24.
T.
Tsuneda
,
H.
Nakano
, and
K.
Hirao
,
J. Chem. Phys.
103
,
6520
(
1995
).
25.
J. F.
Hiller
and
M. L.
Vestal
,
J. Chem. Phys.
77
,
1248
(
1982
).
26.
S. Gerstenkorn and P. Luc, Atlas du Spectre D'Absorption de la Molecule D'Iode (C.N.R.S., Paris, 1978).
27.
J. Malicent, J. Brion, J. Charbonnier, D. Danuont, and C. Parisse, J. Atmos. Chem. (in press).
28.
D. H.
Katayama
,
J. Chem. Phys.
71
,
815
(
1979
).
29.
J. A.
Joens
,
J. Chem. Phys.
101
,
5431
(
1994
).
30.
A.
Sinha
,
D.
Imre
,
J. H.
Goble
, Jr.
, and
J. L.
Kinsey
,
J. Chem. Phys.
84
,
6108
(
1986
).
31.
T.
Tanaka
and
Y.
Morino
,
J. Mol. Spectrosc.
33
,
538
(
1970
).
32.
G. Herzbert, Molecular Spectra and Molecular Structure (Van Nostrand Reinhold, New York, 1966), Vol. 3, p. 225, and Vol. 2, p. 50.
33.
K. P. Huber and G. Herzberg, Molecular Spectra and Molecular Structure, IV. Constants of Diatomic Molecules (Van Nostrand, Reinhold, New York, 1979).
34.
C. E. Moore, Atomic Energy Levels, NSRDS-NBS 35, Vol. 1 (1971).
35.
D. R. Miller, Atomic and Molecular Beam Methods, edited by G. Scoles (Oxford University Press, New York, 1988), Vol. 1, p. 14.
36.
A.
Barbe
,
C.
Secroun
, and
P.
Jouve
,
J. Mol. Spectrosc.
49
,
171
(
1974
).
37.
P. F.
Zittel
and
D. D.
Little
,
J. Chem. Phys.
72
,
5900
(
1980
).
38.
A.
Banichevich
and
S. D.
Peyerimhoff
,
Chem. Phys.
174
,
93
(
1993
).
39.
P. J.
Hay
and
T. H.
Dunning
, Jr.
,
J. Chem. Phys.
67
,
2290
(
1977
).
40.
P. J.
Hay
,
R. T.
Pack
,
R. B.
Walker
, and
E. J.
Heller
,
J. Phys. Chem.
86
,
862
(
1982
).
41.
F.
LeQuéré
and
C.
Leforestier
,
Chem. Phys. Lett.
189
,
537
(
1992
).
42.
D. E.
Freeman
,
K.
Yoshino
,
J. R.
Esmond
, and
W. H.
Parkinson
,
Planet. Space Sci.
32
,
239
(
1984
).
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